Production of aliphatic vinyl ethers by means of acetylene



Patented May UNITEDA STATES `{"RDUCTION F ALIPHATIC VINYL ETHERS i BY MEANS OF ACETYLENE the-Main, Germany `No Drawing. Application September lil, 193'?,

Serial No. 164,498. 1935 This application is a continuation-in-part application of our application Ser. No. 95,036 illed August 8, 1936.v In Example of our copending application Ser. No. 95,036 there is described that a mixture of ethylidene acetals of glucose and fructose can be reacted with acetylene in the presence of calcined zinc acetate and quinoline at elevated temperatures in the liquid phase to form the corresponding vinyl ethers.

We have now found that vinyl ethers are gen erally obtained by treating alcohols with acetylene at elevated temperature in the presence of zinc or cadmium salts of organic acids in the liquid phase. As suitable zinc and cadmium salts there may be mentioned for example the salts of formic acid, acetic acid and butyric acid; the salts of carboxylic acids of high molecular weight, such as alpha-methylvaleric acid, stearic acid, oleic acid, abietic acid and naphthenic acids are especially suitable. In many cases it is preferable, in order to accelerate the reaction and improve the yields, to use the zinc and cadlnium salts in combination with tertiary heterocyclic bases, such as pyridine or quinoline, or with ammonia. The process is applicable generally to compounds containing at least one free alcoholic hydroxyl group. It is especially valuable for the preparation of vinyl ethers from alcohols containing not only hydroxyl groups but also sensitive radicles or groups, such as partially etherifed or acetalized sugars containing at least one free hydroxyl group, as for example tetramethylglucose, betadiacetone-fructcse, mono-acetone-glucose or a mixture of beta-diacetone-fructose and diace tone-glucose, such as is formed by the treatment of cane sugar with acetone and sulphuric acid, or the corresponding methylene, ethylidene and benzylidene acetals, and alcohols containing ester groups, such as hydroxy-fatty acid esters and monoor poly-fatty acid esters of polyhydric alcohols, as for example glycollic acid esters, glycol mono-acetate or glycerine diacetate. The preparation of vinyl others from alcohols containing ester groups in the molecule at the same time is impossible by the known processes in which strong alkalies are used as catalysts because the ester groups are saponii'led by the alkali during the reaction. By the process according to this invention it is possible for the ilrst time also to convert the said alcohols into vinyl ethers by the action of acetylene. l l

The process may be carried out at temper -1 tures of from about 120 to about 200 C., but it is preferable to work at temperatures oi from 150 to 180 C. i

In Germany August 24,

5 claims. (ci. 26o- 488) Example 1 l5 parts of dehydrated cadmium acetate are added to 500 parts of diethylene glycol monoethyl ether and the Whole treated in a pressure-tight` vessel while stirring with a mixture of l part of nitrogen and 2 parts of acetylene under a pressure of from to 20 atmospheres at 180 C. until no further acetylene is absorbed during a period of about'2 hours. The reaction product boils at from about 85 to 110 C. lat a pressure of 12 milllmetres (mercury gauge). In addition to a little unchanged diethylene glycol monoethyl ether it contains mainly the vinyl ether of the same havwhich may be purified in known manner by frac-n tional distillation.

Ezrample 2 10d parts oi glycol monoacetate are treated with acetylene at from 150 to 170 C. in the manner described in Example 1 in the presence of 20 partsvof zinc naphthenate (having a mean molecular Weight of 270). By distilling the reaction product atl a pressure of from 0.1 to 0 3 millimetro (mercury gauge) there is obtained a fraction passing over at from 32 to 40 C. from which by repeated distillation the vinyl ether oi glycol monoacetate may be isolated in pure form. This boils at from 39.5 to 41.5 C. under a pressure of 0.2 millimetre (mercury gauge). The refractive index of the pure Vinyl ether is and the density is d2o=l.012l.

The zinc salt of alphammethylvaleiic acid may be'used as catalyst in the same way instead of zinc naphthenate.

lng point of from 122 to 125 C. at a pressure of from 0.2 to 0.3 mlliimetre (mercury gauge) and a refractive index of are treated with acetylene at from about 148 to about 170 C. in a manner similar to that described in Example 1 in the presence of 7 parts o1' zinc naphthenate (mean molecular weight 270). More than 1 molecular proportion of acetylene is absorbed for each molecular proportion of glycerine dlacetate.

By distilling the reaction product at a pressure of from 0.2 to 0.5 millimetre (mercury gauge) there ilrst passes over at from 64 to 66 C. a product having a refractive index of By further heating at a pressure of 0.2 millimetre (mercury gauge) there is obtained at from 98 to 124 C. yet another fraction having a refractive index of.

consisting of about half of glycerine diacetate monovinyl ether, the remainder being unchangedl initial material.

Example 4 135 parts of concentrated sulphuric acid are allowed to drop slowly while cooling to a mixture of 525 parts of finely powdered sugar and 825 parts of paraldehyde, the temperature not being allowed to rise above 30 C. The reaction mixture is then stirred for from 20 to 30 hours while cooling with ice, poured onto ice and neutralized to litmus by means oi caustic soda solution. 300 parts of butanol are introduced in order to obtain a better separation of the aqueous layer containing sodium sulphate from the layer containing the acetal mixture formed. After allowing to stand for a long time, separation into three layers takes place. The lower layer consists of saturated sodium sulphate solution, the upper layer consists of water and the central layer contains the mixture of the ethylidene acetals of glucose and fructose formed, and also water, paraldehyde and butanol. 'I'he said readily volatile substances are removed therefrom by distilling first under a pressure of from about 50 to 100 millimetres, and then under a pressure of about 5 millimetres (mercury gauge). The acetals remain as a colorless to pale yellow syrup.

39 parts of pure freshly distilled quinoline and 3.5 parts of dehydrated zinc acetate are added to 70 parts of the said acetal mixture. The mixture is then treated at from 153 to 168 C. under pressure with'acetylene diluted with nitrogen. The absorption of acetylene corresponds to the amount calculated for the monovinyl compounds ot diethylidene glucose and ydiethylidene fructose. The vinyl ether mixture formed can be distilled only with difficulty because the ethylidene radicles are split off in part during the distillation by reason of a certain tendency to decomposition of the products. The main fraction boils at from 145 to 156 C. under a pressure of 4 millimetres (mercury gauge) and has the refractive index and is a yellowish to brownish liquid.

What we claim is: 1. In the production of vinyl ethers from a1- cohols and acetylene, the step which comprises treating in the liquid phase an aliphatic alcohol with acetylene at temperatures of between 120 and 200 C. in the presence of a saltof an organic acid and a metal selected from the group consisting of zinc and cadmium.

2. In the production of vinyl ethers from alcohols and acetylene, the step which comprises treating in the liquid phase an aliphatic alcohol with acetylene at temperatures of between 120 and 200 C. in the presence of a salt of an organic acid and a metal selected from the group consisting of zinc and cadmium and a tertiary heterocyclic base.

3. In the production of vinyl etliers from alcohols and acetylene, the step which comprises treating in the liquid phase an acetalized sugar having at least one free hydroxyl group with acetylene at temperatures of between 120 and 200 C. in the presence of a salt of an organic acid and a metal selected from the group consisting oi zinc and cadmium.

4. In the production of vinyl ethers from alcohols and acetylene, the step which comprises treating in the liquid phase a partially esteried polyvalent aliphatic alcohol containing ester groups with acetylene at temperatures of between 120 and 200 C. in the presence of a salt of an organic acid and a metal selected from the group consisting of zinc and cadmium.

5. Ethylene glycol acetate vinyl ether.

WALTER REPPE. OTTO HECHT. 

